Study of the Interactions of Organic Sulfides with Active Species in the Cationic Polymerization of 1,3-Pentadiene

Summary

Different alkyl sulfides (dimethylsulfide, ditertiobutylsulfide and diphenylsulfide) were investigated in the polymerization of 1,3-pentadiene initiated by aluminum trichloride in polar solvent in order to control the polymerization and to study the interaction between the electron donor and the active species. Thus, it was found that dimethylsulfide totally inhibited the polymerization, while thanks to its steric hindrance the polymerization occurred in the presence of ditertiobutylsulfide. However, for this electron donor, a transfer activity was evidenced at room temperature and at 0°C, which contributes to prevent the control of the polymerization. Diphenylsulfide stabilizes a little the active centers with nearly no transfer reaction. However in the studied experimental conditions, the stabilization was not sufficient to obtain a living polymerization.